JP2010254959A - Method for producing granular composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a composition for imparting anti-oxidant properties to the granular. <P>SOLUTION: The method for producing the granular composition includes the steps of: stirring and granulating a mixture containing 3-80 parts weight of phenol compound represented by formula (1) (wherein R<SB>1</SB>is a 1-8C alkyl group; X is a 1-18C n-valent alcohol residue optionally containing a heteroatom, a cyclic group or the heteroatom and the cyclic group; n is an integer of 1-4) and a binder of ≥3 parts weight and <20 parts weight to obtain a granular agglomerate; cracking the granular agglomerate at the temperature which is equal to or higher than 25°C and is 10°C lower than the melting point of the binder by using a cracking machine equipped with a separation mechanism (E) recovering a granule having ≤5 mm particle size and a cracking mechanism (D) to obtain the granule. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a granular composition.

In order to prevent thermal degradation and oxidative degradation, a resin such as polyolefin is blended with an antioxidant imparting composition containing a phenolic antioxidant imparting compound. Since such an antioxidant-imparting composition is generally a powder composition, dust dispersibility has often been a problem, and a granular composition has been provided instead of the powder composition.
Conventionally, as a method for producing a composition for imparting antioxidant properties to granules, for example, a method for producing a granule group described in Patent Document 1 is known (see Patent Document 1).

JP2007-161997

  However, when the composition for imparting antioxidant properties to granules is produced by the stirring granulation method, a granule aggregate in which the granules are aggregated may be obtained, and it is not easy to obtain desired granules.

（式中、Ｒ_１は炭素数１〜８のアルキル基を表し、Ｘはヘテロ原子、環状基、又はヘテロ原子と環状基とを含んでいてもよい炭素数１〜１８のｎ価のアルコール残基を表し、ｎは１〜４の整数を表す。）
で表されるフェノール系化合物３重量部以上８０重量部以下と、バインダー３重量部以上２０重量部未満とを含む混合物を攪拌造粒して得られる顆粒凝集体を、２５℃以上前記バインダーの融点より１０℃低い温度未満で、粒径５ｍｍ以下の顆粒を回収し得る分離機構と解砕機構とを備えた解砕機により解砕して顆粒を得る工程を含む顆粒組成物の製造方法； Under such circumstances, the present inventors have intensively studied, and as a result, have reached the present invention.
That is, the present invention
[1] Formula (1)

(In the formula, R ₁ represents an alkyl group having 1 to 8 carbon atoms, and X represents an n-valent alcohol residue having 1 to 18 carbon atoms which may include a hetero atom, a cyclic group, or a hetero atom and a cyclic group. Represents a group, and n represents an integer of 1 to 4.)
A granule aggregate obtained by stirring and granulating a mixture containing 3 parts by weight or more and 80 parts by weight or less of a phenolic compound represented by the formula, and a melting point of the binder A method for producing a granule composition comprising a step of pulverizing by a pulverizer equipped with a separation mechanism and a pulverization mechanism capable of recovering granules having a particle size of 5 mm or less at a temperature lower than 10 ° C .;

[2] A step of cooling the granule aggregate to 25 ° C. or more and lower than 10 ° C. lower than the melting point of the binder, and a separation mechanism that can collect the cooled granule aggregate and recover granules having a particle size of 5 mm or less. A production method according to [1], comprising a step of obtaining granules by crushing with a crusher equipped with a crushing mechanism;

[3] The production method according to [1] or [2], wherein the separation mechanism is a screen having an opening;
[4] The production method according to any one of [1] to [3], wherein the crushing mechanism is a contact-type shearing mechanism capable of crushing granule aggregates into granules by a reciprocating or rotating plate.
[5] The phenol compound is 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4. , 8,10-tetraoxaspiro [5 · 5] undecane, tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythrityl ester, and bis {3- ( 3-t-butyl-4-hydroxy-5-methylphenyl) propionic acid} triethyleneglycolyl ester, the production method according to any one of [1] to [4], which is at least one compound selected from the group consisting of ;
[6] The binder is represented by the formula (2)
_{(R 2 -Y-S-C} 2 H 4 CO) m -Z (2)
(In the formula, R ₂ represents an alkyl group having 12 to 18 carbon atoms, Y represents a single bond or —C ₂ H ₄ CO ₂ —, m represents an integer of 1 to 4, and Z represents 5 to 5 carbon atoms. 18 represents an m-valent alcohol residue.)
The production method according to any one of [1] to [5], which is a sulfur compound represented by:
[7] The binder is 3,3′-thiodipropionic acid di-n-dodecyl ester, 3,3′-thiodipropionic acid di-n-tetradecyl ester, or 3,3′-thiodipropionic acid di-n. -The production method according to any one of [1] to [6], which is at least one compound selected from the group consisting of octadecyl esters;
Etc. are provided.

  According to the present invention, when producing a granule composition, it is possible to obtain a desired preferable granule. In addition, it is possible to obtain a secondary effect of reducing obstacles and breakage in various production apparatuses based on the impact and contact load caused by the granule aggregates produced when the granule composition is produced by the stirring granulation method. The secondary effect eliminates the need for repair / replacement of various manufacturing apparatuses, and as a result, improves manufacturing efficiency.

Schematic of the stirring granulator used in the examples and comparative examples Schematic diagram of crusher used in Examples and Comparative Examples

(A) Stirring blade (B) Chopper (C) Jacket (D) Rotor (E) Screen

（式中、Ｒ_１は炭素数１〜８のアルキル基を表し、Ｘはヘテロ原子、環状基、又はヘテロ原子と環状基を含んでいてもよい炭素数１〜１８のｎ価のアルコール残基を表し、ｎは１〜４の整数を表す。）
で表されるフェノール系化合物であり、
フェノール系化合物３重量部以上８０重量部以下と、バインダー３重量部以上２０重量部未満とを含む混合物を攪拌造粒して得られた顆粒凝集体を、２５℃以上かつ前記バインダーの融点より１０℃低い温度未満で、粒径５ｍｍ以下の顆粒を回収可能とする分離機構と解砕機構とを備えた解砕機により解砕して顆粒を得る工程を含む製造方法である。 The present invention is a method for producing a granular antioxidant composition comprising a phenolic compound capable of imparting antioxidant properties and a binder,
The phenolic compound is represented by the formula (1)

(In the formula, R ₁ represents an alkyl group having 1 to 8 carbon atoms, and X is a hetero atom, a cyclic group, or an n-valent alcohol residue having 1 to 18 carbon atoms which may contain a hetero atom and a cyclic group. And n represents an integer of 1 to 4.)
A phenolic compound represented by
A granule aggregate obtained by stirring and granulating a mixture containing 3 parts by weight or more and 80 parts by weight or less of a phenolic compound and 3 parts by weight or more and less than 20 parts by weight of a binder is 25 ° C. or more and 10 ° C. from the melting point of the binder. It is a production method including a step of obtaining granules by crushing by a crusher equipped with a separation mechanism and a crushing mechanism that enable recovery of granules having a particle size of 5 mm or less at a temperature lower than 0 ° C.

A phenol type compound is a phenol type compound represented by Formula (1).
R1 in Formula (1) represents an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, an i-propyl group, a t-butyl group, a t-pentyl group, and a t-octyl group. Preferably, a methyl group and t-butyl group are mentioned.
X in Formula (1) represents a C1-C18 n-valent alcohol residue which may contain a hetero atom and / or a cyclic group. Examples of the C1-C18 n-valent alcohol residue that may contain the heteroatom and / or cyclic group include a triethylene glycol residue, a pentaerythritol residue, 3,9-bis ( Examples include residues of 1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5 · 5] undecane. Preferably, a residue of pentaerythritol, a residue of 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5 · 5] undecane can be mentioned. . Here, the alcohol residue means a group obtained by removing H from OH of alcohol.
N in Formula (1) represents the integer of 1-4. Preferably, it is 2 or 4.

  Specific examples of phenolic compounds include 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl]- 2,4,8,10-tetraoxaspiro [5.5] undecane (melting point 110-130 ° C.), tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaeryth Lithyl ester (melting point: 110-130 ° C), bis {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionic acid} triethyleneglycolyl ester (melting point: 76-79 ° C), etc. Can be mentioned.

Typical binders include, for example, partial fatty acid esters of polyhydric alcohols, fatty acid amides, formula (2)
_{(R 2 -Y-S-C} 2 H 4 CO) m -Z (2)
(In the formula, R ₂ represents an alkyl group having 12 to 18 carbon atoms, Y represents a single bond or —C ₂ H ₄ CO ₂ —, m represents an integer of 1 to 4, and Z represents 5 to 5 carbon atoms. 18 represents an m-valent alcohol residue.)
The sulfur type compound etc. which are represented by these are mentioned, The sulfur type compound represented by Formula (2) is used preferably.
R ₂ in Formula (2) represents an alkyl group having 12 to 18 carbon atoms. Examples of the alkyl group having 12 to 18 carbon atoms include lauryl group, myristyl group, palmityl group, stearyl group and the like. Preferably, a lauryl group, a myristyl group, and a stearyl group are mentioned.
Y in the formula (2) represents a single bond or _-C 2 _H 4 CO ₂ - represents a.
Z in Formula (2) represents an m-valent alcohol residue having 5 to 18 carbon atoms. The alcohol residue refers to a group obtained by removing H from OH of alcohol.
Examples of the m-valent alcohol residue having 5 to 18 carbon atoms include lauryl alcohol residue, myristyl alcohol residue, palmityl alcohol residue, stearyl alcohol residue, pentaerythritylic alcohol residue and the like. it can. Preferable examples include lauryl alcohol residue, myristyl alcohol residue, stearyl alcohol residue, and pentaerythritylic alcohol residue.

  Specific examples of the binder include 3,3′-thiodipropionic acid di-n-dodecyl ester (melting point: 40 to 42 ° C.), 3,3′-thiodipropionic acid di-n-tetradecyl ester (melting point: 49 -54 ° C), 3,3'-thiodipropionic acid di-n-octadecyl ester (melting point 65-67 ° C), tetrakis (3-dodecylthiopropionic acid) pentaerythrityl ester (melting point about 46 ° C), etc. be able to.

In order to produce a granule composition by the production method of the present invention, first, a mixture containing 3 parts by weight or more and 80 parts by weight or less of a phenolic compound and 3 parts by weight or more and less than 20 parts by weight of a binder is granulated with stirring. Preferably, the phenolic compound is 3 parts by weight or more and 50 parts by weight or less, and the binder is 3 parts by weight or more and less than 20 parts by weight. More preferably, the phenolic compound is 3 parts by weight or more and 50 parts by weight or less, and the binder is 10 parts by weight or more. A mixture containing less than 20 parts by weight is stirred and granulated.
Further, the mixing ratio of the phenolic compound and the binder contained in the mixture is usually 5: 1 to 1: 5, preferably 2: 1 to 1: 4.

In addition, as long as the said mixture has the effect of this invention, a neutralizer, a phosphorus antioxidant imparting compound, a hindered amine light stabilizer, an ultraviolet absorber, a metal soap, an antistatic agent, an antiblocking agent, a pigment, It may contain one or more additives such as flame retardants, fillers, nucleating agents, lubricants, plasticizers, processing aids, foaming agents, emulsifiers, brighteners, phenolic antioxidant compounds other than the phenolic compounds. Good.
The amount of the additive used is preferably 3 to 90% by weight, more preferably 10 to 85% by weight, still more preferably 25 to 85% by weight, based on the total weight of the mixture containing the phenolic compound and the binder. It is.

<Neutralizing agent>
Synthetic hydrotalcite, natural hydrotalcite, neutralizing agents such as calcium hydroxide;
<Phosphorus antioxidant compound>
Tris (2,4-di-t-butylphenyl) phosphite (melting point 183 to 187 ° C.), bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite (melting point 160 to 180 ° C.), bis (2 , 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (melting point 237-238 ° C.), bis (2,4-di-cumylphenyl) pentaerythritol diphosphite (melting point 221-230 ° C.), tetrakis (2, 4-Di-t-butylphenyl) -4,4′-biphenylene diphosphonite (melting point 75 ° C.), 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4 , 8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine (melting point 115 ° C.), (2,4-di-cumylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene diphosphonite (melting point 75-90 ° C.), bis- [2,4- Phosphorous antioxidants such as di-t-butyl, (6-methyl) phenyl] ethyl phosphite (melting point 89-92 ° C.);

<Hindered amine light stabilizer>
Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (melting point 81-86 ° C.), bis (2,2,6,6-tetramethyl-4-piperidyl) ester, 2,2,6 , 6-Tetramethyl-4-piperidyl methacrylate (melting point: 58 ° C.), poly [{6- (1,1,3,3, -tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl } {(2,2,6,6-tetramethyl-4-piperidyl) imino} -1,6-hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] (melting point 100 Hindered amine light stabilizers such as ~ 135 ° C);

<Ultraviolet absorber>
2-hydroxy-4-n-octyloxy benzophenone (melting point 45 ° C. or higher), 2- (2H-benzotriazol-2-yl) -4,6-di-t-pentylphenol (melting point 77 ° C. or higher), 2- [ 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl-]-5- (octyloxy) phenol (melting point 87-89 ° C.), 2- (2-hydroxy-5 -Methylphenyl) benzotriazole (melting point 127 ° C), 2- (3-t-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole (melting point 137 ° C), 2,4-di-t- UV absorbers such as butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate (melting point 192 ° C.);

<Metal soap>
Metal soaps such as fatty acid metal salts such as calcium stearate;

<Antistatic agent>
Quaternary ammonium salt type cationic surfactant, betaine type amphoteric surfactant, alkyl phosphate type anionic surfactant, primary amine salt, secondary amine salt, tertiary amine salt, quaternary Cationic surfactants such as amine salts and pyridine derivatives,
Sulfated oil, soap, sulfated ester oil, sulfated amide oil, sulfated olefin salt of olefin, fatty alcohol sulfate, alkyl sulfate, fatty acid ethyl sulfonate, alkyl naphthalene sulfonate, alkyl benzene sulfonate , Anionic surfactants such as oxalate ester sulfonate and phosphate ester salt,
Partially fatty acid ester ethylene oxide adduct of polyhydric alcohol, fatty alcohol ethylene oxide adduct, fatty acid ethylene oxide adduct, fatty amino or fatty acid amide ethylene oxide adduct, alkylphenol ethylene oxide adduct, polyhydric alcohol Nonionic surfactants such as ethylene oxide adducts of partial fatty acid esters and polyethylene glycol,
Antistatic agents such as amphoteric surfactants such as carboxylic acid derivatives and imidazoline derivatives;

<Anti-blocking agent>
Inorganic antiblocking agents such as aluminum silicate, synthetic silica, natural silica, zeolite, kaolin and diatomaceous earth, or organic antiblocking agents such as cross-linked polymethylmethacrylic acid;

<Pigment>
Carbon black, titanium oxide, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, perylene or perine pigment, quinophthalone pigment, diketopyrrolo-pyrrole pigment, dioxazine pigment, disazo condensation pigment and benzimidazolone pigment Pigments such as

<Flame Retardant>
Flame retardants such as decabromobiphenyl, antimony trioxide, phosphorus flame retardant, aluminum hydroxide;

<Flame Retardant>
Flame retardants such as decabromobiphenyl, antimony trioxide, phosphorus flame retardant, aluminum hydroxide;

<Filler>
Fillers such as calcium carbonate, silicate, glass fiber, talc, kaolin, mica, barium sulfate, carbon black, carbon fiber, zeolite, metal powder, metal oxide;

<Nucleating agent>
α-Naphthalenesulfonic acid Na salt, α-naphthalenesulfonic acid Mg salt, α-naphthalenesulfonic acid Ca salt, α-naphthalenesulfonic acid Al salt, 8-aminonaphthalenesulfonic acid Na salt, benzenesulfonic acid Na salt, Mg salt of benzenesulfonic acid, Ca salt of benzenesulfonic acid, Al salt of benzenesulfonic acid, Ca salt of 2,5-dichlorobenzenesulfonic acid, Mg salt of 2,5-dichlorobenzenesulfonic acid, m- Ca salt of xylenesulfonic acid, Mg salt of m-xylenesulfonic acid, benzoic acid (melting point 122 ° C.), p-isopropylbenzoic acid, ot-butylbenzoic acid, pt-butylbenzoic acid, monophenylacetic acid ( Melting point 77 ° C), diphenylacetic acid, Li salt of diphenylacetic acid, Al salt, Na salt, Na salt of diphenylacetic acid, diphenylacetic acid g salt, diphenylacetic acid Ca salt, diphenylacetic acid Ba salt, diphenylacetic acid Al salt, phenyldimethylacetic acid, phenyldimethylacetic acid Li salt, phenyldimethylacetic acid Na salt, phenyldimethylacetic acid Mg salt, phenyldimethylacetic acid Ca salt, Ba salt of phenyldimethylacetic acid, Mg salt of phthalic acid, oxalic acid (melting point 185 ° C.), Li salt of oxalic acid, Na salt of oxalic acid, Mg salt of oxalic acid, Ca salt of oxalic acid, oxalic acid Ba salt of glutaric acid (melting point 95-99 ° C.), Li salt of glutaric acid, Na salt of glutaric acid, Mg salt of glutaric acid, Ca salt of glutaric acid, Ba salt of glutaric acid, adipic acid (melting point 151- 153 ° C.), suberic acid, Li salt of suberic acid, Na salt of suberic acid, Mg salt of suberic acid, Ca salt of suberic acid, Ba salt of suberic acid, Vacic acid, sebacic acid Li salt, sebacic acid Na salt, sebacic acid Mg salt, sebacic acid Ca salt, sebacic acid Al salt, diphenylphosphinic acid (melting point 193-196 ° C.), diphenylphosphinic acid Li salt Na salt of diphenylphosphinic acid, K salt of diphenylphosphinic acid, Ca salt of diphenylphosphinic acid, Mg salt of diphenylphosphinic acid, Al salt of diphenylphosphinic acid, Li salt of 4,4′-dichlorodiphenylphosphinic acid, 4 , 4′-dimethyldiphenylphosphinic acid Na salt, dinaphthylphosphinic acid, dinaphthylphosphinic acid Li salt, dinaphthylphosphinic acid Na salt, dinaphthylphosphinic acid Mg salt, dinaphthylphosphinic acid Ca salt, di Nucleating agents such as Al salt of naphthylphosphinic acid;

<Phenolic antioxidant imparting compounds other than the present phenolic antioxidant imparting compound>
2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (melting point: 130 ° C. or higher), 2- [1- (2-hydroxy-3, 5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate (melting point: 119 ° C.), 1,3,5-trimethyl-2,4,6-tris (3,5- Di-t-butyl-4-hydroxybenzyl) benzene (melting point 240-245 ° C.), tris (3,5-di-t-butyl 4-hydroxybenzyl) isocyanurate (melting point 218-223 ° C.), 1,3, 5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (mp 159-162) ° C), 2, '-Methylenebis (6-t-butyl-4-methylphenol) (melting point 128 ° C or higher), 4,4'-butylidenebis (6-t-butyl-3-methylphenol) (melting point 209 ° C or higher), 4,4 '-Thiobis (6-t-butyl-3-methylphenol) (melting point 160 ° C. or higher), n-octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate (melting point 50 to 55) ° C), 2,6-di-t-butyl-4-methylphenol (melting point 69 ° C (freezing point), 2,2-thio-diethylene-bis- [3- (3,5-di-t-butyl-4 Phenolic antioxidant imparting compounds such as (hydroxyphenyl) propionate] (melting point 63 ° C. or higher);
Etc.

In order to produce a granule composition by the production method of the present invention, as described above, a mixture containing 3 to 80 parts by weight of a phenolic compound and 3 to 20 parts by weight of a binder is first stirred. Grained.
The stirring granulator used in the stirring granulation step usually has a stirring blade inside the stirring tank, and is usually 30 mm or less, preferably between the stirring blade and the inner wall surface of the stirring tank. And an internal stirring granulator having a clearance of about 0.1 mm to 5 mm.
Typical stirring granulators include, for example, a high speed mixer (stirring tumbling granulator), a Henschel mixer (high speed stirring granulator), vertical granulator, pharmamatrix, super mixer, GRAL-Gral, Shugi mixer, Examples include vertical mixers such as high speedrs and new speed kneaders, horizontal mixers such as Redige mixers, Spartan rewinders, and pin mixers. Preferably, a high speed mixer is mentioned.

The blade tip of the stirring blade that the stirring granulator has in the stirring tank may be designed as appropriate. For example, in the case of a high-speed mixer, it is inclined toward the center (for example, 10 ° to A shape in which the mixture is scooped up in the center and the mixture does not stay in the corners of the bottom and the wall surface can be mentioned as a preferable example.
The blade tip speed of the stirring blade that the stirring granulator has in the stirring tank varies depending on the shape, and examples thereof include 2 m / s or more and 40 m / s or less. Preferably, 4 m / s or more and 10 m / s or less are mentioned. In addition, when the agitation granulator has a chopper on the tank wall of the agitation tank to prevent segregation of the mixture, the blade tip speed of the chopper varies depending on the shape, but may be 2 m / s or more and 40 m / s or less, for example. it can. Preferably, 5 m / s or more and 30 m / s or less are mentioned.

The capacity of the raw material that is supplied to the inside of the stirring tank provided in the stirring granulator and becomes a mixture containing the phenolic compound and the binder can be appropriately changed. For example, in the case of a high-speed mixer, What is necessary is just to make it occupy the volume of 30% or more and 60% or less with respect to the whole capacity | capacitance of a stirring tank.
When supplying a raw material to be a mixture containing a phenolic compound and a binder into the stirring tank provided in the stirring granulator, for example, each of the raw materials to be a mixture containing a phenolic compound and a binder is previously stored. Although it may mix with mixers, such as a mixer and a blender, and this mixture may be supplied to the said stirring granulator, it is preferable to supply each of the said raw material to the said stirring granulator simultaneously or sequentially.

  As temperature setting at the time of carrying out stirring granulation of the mixture containing a phenol type compound and a binder, the range below the temperature 10 degreeC higher than the melting point of a binder and 20 degreeC higher than the melting point of a binder can be mentioned, for example. Preferably, the temperature is 10 ° C. lower than the melting point of the binder and 10 ° C. higher than the melting point of the binder. The temperature setting may be performed by using, for example, a heating means included in a stirring granulator, and specifically includes a method in which the temperature is raised through a heating medium through a jacket of the stirring granulator.

In the production method of the present invention, a granule aggregate obtained by stirring and granulating a mixture containing a phenolic compound and a binder is granulated with a particle size of 5 mm or less at a temperature of 25 ° C. or more and less than 10 ° C. lower than the melting point of the binder. A step of obtaining granules by crushing by a crusher equipped with a separation mechanism and a crushing mechanism that enable recovery of the sucrose.
The means for bringing the granule aggregate to 25 ° C. or higher and lower than 10 ° C. lower than the melting point of the binder is not particularly limited, and examples thereof include cooling methods such as air cooling and water cooling. In addition, a granule aggregate obtained by stirring and granulating a mixture containing the phenolic compound and the binder is obtained, and this is allowed to stand at a temperature of 25 ° C or higher and 10 ° C lower than the melting point of the binder. Even when the granule aggregate reaches a temperature of 25 ° C. or more and 10 ° C. lower than the melting point of the binder due to the sufficient time until it is supplied to the crusher incorporating the separation mechanism and the crushing mechanism, It may be regarded as a simple cooling method.

  The separation mechanism provided in the crusher may be any as long as it can collect granules having a particle size of 5 mm or less. As a typical separation mechanism, for example, a screen having an opening that makes it possible to collect the desired particle diameter can be exemplified. Here, “comprising” means (1) that the separation mechanism is integrally included in the crusher main body, so that the crusher has the separation mechanism internally, and the crusher has a built-in crusher. It means not only the presence mode in which the step of separating the granule aggregate and the granule by the separation mechanism proceeds in parallel or continuously with the step of crushing the granule aggregate by the crushing mechanism, (2) Since the separation mechanism is additionally installed outside the crusher main body, the crusher is externally provided with the separation mechanism, and the granule aggregate is disintegrated by the crushing mechanism built in the crusher. The present invention also includes an embodiment in which the step of separating the granule aggregate and the granule by the separation mechanism proceeds discontinuously after the crushing step. Further, the “opening” means an eye or an opening (granular passage portion) of the screen. Examples of the size of “eyes or openings” include about 2 to 5 mm.

As a crushing mechanism with which a crusher is equipped, the contact-type shear mechanism etc. which can crush a granule aggregate into a granule by the plate which reciprocates or rotates can be mentioned, for example.
The temperature setting when the granule aggregate is crushed by such a pulverizer is in the range of 25 ° C. or more and less than 10 ° C. lower than the melting point of the binder. The temperature setting may be performed by using, for example, a heating or cooling means included in the crusher, and specific examples include a method of adjusting the temperature through a heating medium through a jacket of the crusher.

  Examples of the crusher that can be used in the production method of the present invention (also generally referred to as a crusher, a crusher, etc.) include, for example, an oscillator (manufactured by Fukae Powtech), a flake crusher (Hosokawa Micron). ), Disintegrator (Hosokawa Micron), Power Mill (Fuji Powdal), Quick Mill (Seishin), Feather Mill (Hosokawa Micron), Cutter Mill (Masuno Sangyo, Masuko Sangyo) Sho Industry Co., Ltd.) and Bex Mill (Hosokawa Micron Co., Ltd.). Preferably, an oscillator and a flake crusher are used.

  The oscillator will be described in more detail as a typical crusher. The oscillator used in the examples of the present application (specifically, in the case of aiming at the desired granule diameter) includes a rotor and a screen, and is usually 10 mm or less between the rotor and the screen. Preferably, the clearance is about 1 mm or more and 5 mm or less. By reciprocating the rotor, the granule aggregate is crushed to obtain granules. Examples of the reciprocating speed of the rotor include a tip speed of 0.1 m / s to 1 m / s, 30 reciprocations / min to 300 reciprocations / min, and the like.

The granule thus obtained has a particle size of substantially 5 mm or less, and may be used as a product as it is. In addition, when finishing to the product which has only the said desired particle size more accurately, as needed, the fine powder contained in the obtained granule is used, for example, a sieve with an opening of about 0.1 mm to 2 mm. Then, a process to be removed may be added.
The removed fine powder may be used again as a raw material for the production method of the present invention.

  The granule composition produced by the production method of the present invention is used by blending with a resin such as polyolefin, for example. Examples of the blending ratio of the granule composition and the resin of the present invention include a ratio of blending a granule composition of 5 parts by weight or less with respect to 100 parts by weight of the resin, specifically, The blending ratio is 0.005 part by weight or more and 5 parts by weight or less, preferably 0.01 part by weight or more and 2 parts by weight or less, more preferably 0.01 part by weight or more and 1 part by weight or less.

In the resin composition obtained by blending the granule composition of the present invention and the resin, the resin is preferably a thermoplastic resin.
Here, the thermoplastic resin is not particularly limited as long as it is a commercially available resin. For example, polypropylene resin such as ethylene-propylene copolymer, polyethylene resin (high density polyethylene (HD-PE), low Density polyethylene (LD-PE), linear low density polyethylene (LLDPE), etc.), methylpentene polymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, polystyrenes (poly (p-methylstyrene) ), Polystyrene such as poly (α-methylstyrene), acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, special acrylic rubber-acrylonitrile-styrene copolymer, acrylonitrile-chlorinated polyethylene-styrene copolymer Styrene-butadiene copolymer Body), chlorinated polyethylene, polychloroprene, chlorinated rubber, polyvinyl chloride, polyvinylidene chloride, methacrylic resin, ethylene-vinyl alcohol copolymer, fluororesin, polyacetal, grafted polyphenylene ether resin, polyphenylene sulfide resin, polyurethane , Polyamide, polyester resin (eg, polyethylene terephthalate, polybutylene terephthalate, etc.), polycarbonate, polyacrylate, polysulfone, polyether ether ketone, polyether sulfone, aromatic polyester resin, diallyl phthalate prepolymer, silicone resin, 1,2-polybutadiene , Polyisoprene, butadiene / acrylonitrile copolymer, ethylene-methyl methacrylate copolymer, etc., and moldability From the viewpoint of goodness, polyethylene-based resins, polypropylene-based resins, and polystyrenes are preferable.

  Here, the polypropylene-based resin means a polyolefin containing a structural unit derived from propylene. Specifically, a crystalline propylene homopolymer, a propylene-ethylene random copolymer, a propylene-α-olefin random copolymer. Polypropylene block comprising a polymer, a propylene-ethylene-α-olefin copolymer, a propylene homopolymer component or a copolymer component mainly composed of propylene, and a copolymer component of propylene and ethylene and / or α-olefin A copolymer etc. are mentioned.

  In the present invention, when a polypropylene resin is used as the thermoplastic resin, the polypropylene resin may be used alone or in a blend of two or more.

  Examples of the α-olefin include α-olefins having 4 to 12 carbon atoms. For example, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-octene, Decene etc. are mentioned, Preferably 1-butene, 1-hexene, 1-octene is mentioned.

  Examples of the propylene-α-olefin random copolymer include a propylene-1-butene random copolymer, a propylene-1-hexene random copolymer, a propylene-1-octene random copolymer, and the like.

  Examples of the propylene-ethylene-α-olefin copolymer include propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, and propylene-ethylene-1-octene copolymer. It is done.

  As a copolymer component mainly composed of propylene in a propylene homopolymer component or a copolymer component mainly composed of propylene and a polypropylene block copolymer composed of a copolymer component of propylene and ethylene and / or α-olefin Examples thereof include a propylene-ethylene copolymer component, a propylene-1-butene copolymer component, a propylene-1-hexene copolymer component, and the like, and a copolymer component of propylene and ethylene and / or an α-olefin. As, for example, propylene-ethylene copolymer component, propylene-ethylene-1-butene copolymer component, propylene-ethylene-1-hexene copolymer component, propylene-ethylene-1-octene copolymer component, propylene -1-butene copolymer component, propylene-1-hexene copolymer component , Propylene-1-octene copolymer component and the like. The content of ethylene and / or α-olefin having 4 to 12 carbon atoms in the copolymer component of propylene and ethylene and / or α-olefin is usually 0.01 to 20% by weight.

  Examples of the polypropylene block copolymer comprising a propylene homopolymer component or a copolymer component mainly composed of propylene and a copolymer component of propylene and ethylene and / or α-olefin include, for example, a propylene-ethylene block Copolymer, (propylene)-(propylene-ethylene) block copolymer, (propylene)-(propylene-ethylene-1-butene) block copolymer, (propylene)-(propylene-ethylene-1-hexene) block Copolymer, (propylene)-(propylene-1-butene) block copolymer, (propylene)-(propylene-1-hexene) block copolymer, (propylene-ethylene)-(propylene-ethylene-1-butene) ) Block copolymer, (propylene-ethylene)-(propylene (Ethylene-1-hexene) block copolymer, (propylene-ethylene)-(propylene-1-butene) block copolymer, (propylene-ethylene)-(propylene-1-hexene) block copolymer, (propylene- 1-butene)-(propylene-ethylene) block copolymer, (propylene-1-butene)-(propylene-ethylene-1-butene) block copolymer, (propylene-1-butene)-(propylene-ethylene-) 1-hexene) block copolymer, (propylene-1-butene)-(propylene-1-butene) block copolymer, (propylene-1-butene)-(propylene-1-hexene) block copolymer, etc. Can be mentioned.

  In the present invention, when a polypropylene resin is used as the thermoplastic resin, preferably, a crystalline propylene homopolymer, a propylene homopolymer component or a copolymer component mainly composed of propylene, and propylene, ethylene and / or carbon atoms. A polypropylene-based block copolymer composed of a copolymer component of α-olefin of 4 to 12 is used, more preferably a propylene homopolymer component or a copolymer component mainly composed of propylene, propylene and ethylene, and A polypropylene block copolymer composed of a copolymer component of an α-olefin having 4 to 12 carbon atoms is used.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

<Material>
In the examples, the following raw materials were used.
Component A (phenolic antioxidant (1)): 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl ] -2,4,8,10-tetraoxaspiro [5.5] undecane "Sumilyzer GA-80 (registered trademark)" (manufactured by Sumitomo Chemical Co., Ltd.)
Component B (binder): 3,3′-thiodipropionic acid di-n-tetradecyl ester “Sumilyzer TPM (registered trademark)” (manufactured by Sumitomo Chemical Co., Ltd.) (melting point: 51 ° C.)
Component C: Calcium stearate (manufactured by Shinagawa Chemical)
Component D: Tris (2,4-di-t-butylphenyl) phosphite “Irgaphos 168 (registered trademark)” (manufactured by Ciba Specialty Chemicals)
Component E: Fine powder talc “Micron White 5000S (registered trademark)” (manufactured by Hayashi Kasei)
Component F: Oleic acid amide

Example 1
A 100 L high-speed mixer (Fukae Powtech: Model No. FS-100), Component A 0.6 kg (3.9 parts by weight), Component B 1.7 kg (11.5 parts by weight), and Component C (7.7 weights) Part), component D (15.4 parts by weight), component E (46.1 parts by weight) and component F (15.4 parts by weight) were added (total 15 kg).
By passing hot water of 60 ° C. through the jacket of the high speed mixer, the temperature of the stirring tank included in the high speed mixer is increased, and then the rotation speed of the stirring blade included in the stirring tank of the high speed mixer is 165 rpm ( After setting the blade tip speed to 6 m / s) and the chopper speed to 1500 rpm (blade tip speed 10 m / s), the high speed mixer was operated for about 40 minutes while maintaining this state.
In this way, 13.6 kg of granule aggregate (granular aggregate temperature of 47 ° C. at the end of stirring granulation) obtained by stirring and granulating the mixture of the raw materials was obtained.
The granule aggregate thus obtained was allowed to stand, and the temperature of the granule aggregate was cooled to room temperature (about 30 ° C.). After cooling, this was put into an oscillator (manufactured by Fukae Powtech: Model No. MF-3) equipped with a screen having an opening of 4 mm size.
After confirming that the clearance between the rotor of the oscillator and the screen is 1 mm or more and 5 mm or less, the temperature of the granule aggregate is maintained at about 30 ° C. without increasing the temperature of the rotor. After setting the reciprocating speed of the rotor to 0.37 m / s and 110 reciprocating / min as the tip speed, the oscillator was operated for about 1 minute while maintaining this state.
In this way, the granule aggregate was crushed by an oscillator to obtain granules (particle size 4 mm or less, yield: 99.4%).
The yield calculation method is
Yield = (weight of granule obtained by crushing with oscillator) /
(Weight of granule aggregate charged in the oscillator) × 100
It is.
It should be noted that there are no obstacles / breakage in various manufacturing devices (specifically, deformation in the screen of the oscillator, deformation in the reciprocating or rotating plate of the oscillator) based on the impact / contact load caused by the granular aggregates, Repair and replacement of various manufacturing equipment is not required, resulting in improved manufacturing efficiency.

(Example 2)
Component A 0.7 kg (4.5 parts by weight), Component B 2.1 kg (13.7 parts by weight), Component C (9.1 parts by weight), Component D (18.2 parts by weight) and Component E (54 (5 parts by weight) was added.
By passing hot water of 60 ° C. through the jacket of the high-speed mixer, the temperature of the stirring tank included in the high-speed mixer is increased, and then the rotation speed of the stirring blade included in the stirring tank of the high-speed mixer is 165 rpm ( After setting the blade tip speed to 6 m / s) and the chopper speed to 1500 rpm (blade tip speed 10 m / s), the high speed mixer was operated for about 1 minute 30 seconds while maintaining this state.
Thus, 12.0 kg of granule aggregates obtained by stirring and granulating the mixture of the raw materials (product temperature 51 ° C. at the end of stirring granulation) was obtained.
The granule aggregate thus obtained was left standing and cooled to room temperature (30 ° C.). After cooling, this was put into an oscillator (manufactured by Fukae Powtech: Model No. MF-3) equipped with a screen having an opening having an opening size of 4 mm.
After confirming that the clearance between the rotor of the oscillator and the screen is not less than 1 mm and not more than 5 mm, the rotor is reciprocated while maintaining the product temperature without increasing the temperature of the rotor. The speed was set to 0.37 m / s and 110 reciprocations per minute as the tip speed, and then the oscillator was operated for about 1 minute while maintaining this state.
In this way, the granule aggregate was crushed by an oscillator to obtain granules (granule diameter of 4 mm or less, yield: 99.1%).
It should be noted that there are no obstacles / breakage in various manufacturing devices (specifically, deformation in the screen of the oscillator, deformation in the reciprocating or rotating plate of the oscillator) based on the impact / contact load caused by the granular aggregates, Repair and replacement of various manufacturing equipment is not required, resulting in improved manufacturing efficiency.

(Example 3)
To a 2500 L high-speed mixer (Fukae Pautech: model number FS-GC-2500J), component A 15 kg (3.8 parts by weight), component B 45 kg (11.6 parts by weight), and component C (7.7 parts by weight) The raw materials (total 392 kg) consisting of Component D (15.4 parts by weight), Component E (46.2 parts by weight) and Component F (15.4 parts by weight) were charged.
By passing hot water of 60 ° C. through the jacket of the high-speed mixer, the temperature of the stirring tank included in the high-speed mixer is increased, and then the rotation speed of the stirring blade included in the stirring tank of the high-speed mixer is 61 rpm ( After setting the blade tip speed to 6 m / s) and the chopper speed to 1500 rpm (blade tip speed 24 m / s), the high speed mixer was operated for about 50 minutes while maintaining this state.
In this manner, 389 kg of granule aggregates (product temperature at the end of stirring granulation) obtained by stirring and granulating the mixture of the raw materials was obtained.
The granule aggregate thus obtained was allowed to stand and cooled to 40 ° C. or lower. After cooling, it was put into an oscillator (made by Fukae Powtech: Model No. MF-6) equipped with a screen having an opening having a size of 4 mm.
After confirming that the clearance between the rotor of the oscillator and the screen is not less than 1 mm and not more than 5 mm, the rotor is then maintained while maintaining the temperature below the product temperature without increasing the temperature of the rotor. Was set to 0.37 m / s and 110 reciprocations per minute as the tip speed, and then the oscillator was operated for about 25 minutes while maintaining this state.
In this way, the granule aggregate was pulverized with an oscillator to obtain granules (a granule diameter of 4 mm or less, the yield was 99.9%).
It should be noted that there are no obstacles / breakage in various manufacturing devices (specifically, deformation in the screen of the oscillator, deformation in the reciprocating or rotating plate of the oscillator) based on the impact / contact load caused by the granular aggregates, Repair and replacement of various manufacturing equipment is not required, resulting in improved manufacturing efficiency.

(Comparative Example 1)
To a 100 L high-speed mixer (Fukae Pautech: Model FS-100), Component A 0.6 kg (3.9 parts by weight), Component B 1.7 kg (11.5 parts by weight), and Component C (7.7 weights) Part), component D (15.4 parts by weight), component E (46.1 parts by weight) and component F (15.4 parts by weight) were added (total 15 kg).
By passing hot water of 60 ° C. through the jacket of the high-speed mixer, the temperature of the stirring tank included in the high-speed mixer is increased, and then the rotation speed of the stirring blade included in the stirring tank of the high-speed mixer is 165 rpm ( After setting the blade tip speed to 6 m / s) and the chopper speed to 1500 rpm (blade tip speed 10 m / s), the high speed mixer was operated for about 40 minutes while maintaining this state.
In this way, 14.0 kg of granule aggregate obtained by stirring and granulating the mixture of the raw materials (product temperature of 46 ° C. at the end of stirring granulation) was obtained.
The thus obtained granule aggregate was charged into an oscillator (manufactured by Fukae Powtech: Model No. MF-3) equipped with a screen having an opening having an opening size of 4 mm while maintaining the product temperature.
After confirming that the clearance between the rotor of the oscillator and the screen is 1 mm or more and 5 mm or less, the temperature of the rotor is then raised, and the reciprocating speed of the rotor is increased while maintaining the product temperature. After setting the tip speed to 0.37 m / s and 110 reciprocations / minute, the oscillator was operated for about 2 minutes while maintaining this state.
In this way, the granule aggregate was crushed by an oscillator to obtain a granule (a granule diameter of 4 mm or less). The yield was as low as 59.3%.
In addition, failures and damages have occurred in various manufacturing devices (specifically, deformation of the screen of the oscillator, reciprocation of the oscillator, or deformation of the rotating plate) based on the impact and contact load caused by the granular aggregates. As a result, it was necessary to repair and replace various manufacturing equipment, resulting in a decrease in manufacturing efficiency.

  According to the present invention, desired granules can be obtained. In addition, secondary effects such as reducing obstacles and breakage in various production equipment based on impact and contact load due to granule aggregates produced when the granule composition is produced by agitation granulation method can be obtained, and repair of various production equipment・ No need for replacement, improving manufacturing efficiency.

Claims (7)

Formula (1)

(In the formula, R ₁ represents an alkyl group having 1 to 8 carbon atoms, and X represents an n-valent alcohol residue having 1 to 18 carbon atoms which may include a hetero atom, a cyclic group, or a hetero atom and a cyclic group. Represents a group, and n represents an integer of 1 to 4.)
A granule aggregate obtained by stirring and granulating a mixture containing 3 parts by weight or more and 80 parts by weight or less of a phenolic compound represented by the formula, and a melting point of the binder A method for producing a granule composition comprising a step of obtaining granules by crushing with a crusher equipped with a separation mechanism capable of recovering granules having a particle size of 5 mm or less at a temperature lower than 10 ° C. and a crushing mechanism. A step of cooling the granular aggregate to 25 ° C. or more and lower than 10 ° C. lower than the melting point of the binder, and a separation mechanism and a crushing mechanism capable of recovering the cooled granular aggregate to granules having a particle size of 5 mm or less; The manufacturing method of Claim 1 including the process of crushing by the crusher provided with this, and obtaining a granule. The manufacturing method according to claim 1, wherein the separation mechanism is a screen having an opening. The production method according to any one of claims 1 to 3, wherein the crushing mechanism is a contact-type shearing mechanism capable of crushing the granule aggregate into granules by a reciprocating or rotating plate. The phenol compound is 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8, 10-tetraoxaspiro [5.5] undecane, tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythrityl ester, and bis {3- (3-t The production method according to any one of claims 1 to 4, which is at least one compound selected from the group consisting of -butyl-4-hydroxy-5-methylphenyl) propionic acid} triethyleneglycolyl ester. The binder is of formula (2)
_{(R 2 -Y-S-C} 2 H 4 CO) m -Z (2)
(In the formula, R ₂ represents an alkyl group having 12 to 18 carbon atoms, Y represents a single bond or —C ₂ H ₄ CO ₂ —, m represents an integer of 1 to 4, and Z represents 5 to 5 carbon atoms. 18 represents an m-valent alcohol residue.)
The production method according to claim 1, which is a sulfur compound represented by the formula: Binder is 3,3′-thiodipropionic acid di-n-dodecyl ester, 3,3′-thiodipropionic acid di-n-tetradecyl ester or 3,3′-thiodipropionic acid di-n-octadecyl ester The production method according to claim 1, which is at least one compound selected from the group consisting of:

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